Preparation and characterization of carboxylterminated poly (butadiene-co-acrylonitrile) -epoxy resin prepolymers for fusion-bonded-epoxy powder coating

Liquid carboxyl-terminated poly(butadiene-co-acrylonitrile)(CTBN)-epoxy resin(EP) prepolymers were prepared with different contents of CTBN.The chemical reactions between EP and CTBN were characterized by Fourier ransform infrared(FTIR) spectroscopy and gel permeation chromatography(GPC).The scanning electron micrograph(SEM) and dynamic mechanical analysis(DMA) of curing films showed phase separation,and the rubber particles were finely dispersed in the epoxy matrix.Mechanical properties analysis of curing films showed that impact strength and elongation at break increased significantly upon the addition of CTBN,indicating good toughness of the modified epoxy resins.Thermogravimetric analysis(TGA) showed that the incorporation of CTBN had little effect on the thermal stability of EP.Fusion-bonded-epoxy(FBE) powder coatings modified with CTBN-EP prepolymers were prepared.The experimental results demonstrate the ability of CTBN-EP prepolymers,toughening technology to dramatically enhance the flexibility and impact resistance of FBE coatings without compromising other key properties such as corrosion protection.     

Structural characteristics and properties of PU-modified TDE-85/MeTHPA epoxy resin

Diglycidyl-4,5-epoxycyclohexane-1,2-dicarboxylate (TDE-85)/methyl tetrahydro-phthalic anhydride (MeTHPA) epoxy resin was modified by polyurethane(PU), and its structural characteristics and properties were studied by infrared spectrum analysis (IR), scanning electronic microscopy (SEM), mechanics testing and thermogravimetric analysis (TG). The results indicate that epoxy polymeric network I and polyurethane polymeric network II are formed in the PU-modified TDE-85/MeTHPA epoxy resin. Meanwhile the PU-modified TDE-85/MeTHPA resins have heterogeneous structure. The miscibility between epoxy (EP) and polyurethane (PU) as well as the phase size are dominantly determined by the mass fraction of polyurethane prepolymer (PUP) in the EP/PU blends. With the increase of PUP mass fraction, the tensile strength, impact strength and thermal stability of the PU-modified TDE-85/MeTHPA epoxy resin all firstly exhibit increasing tendency, and decrease after successively reaching their maxima. When the number-average molecular mass of PPG is 1 000 and the mass fraction of PUP is 15%, the tensile strength, impact strength and thermal stability of materials obtained, compared with TDE-85/MeTHPA epoxy resin, are improved obviously.     

有机累托面/聚烯烃弹性体协同增韧补强聚丙烯的研究

分别研究了有机累托石粘土(OREC)、聚烯烃弹性体(POE)改性的聚丙烯(PP)以及POE／OREC／PP三元改性体系的冲击强度、拉伸强度及断裂伸长率。结果表明，在粘土添加量为2phr时(per hundred resin)可对PP同时实施增强、增韧。OREC与POE有协同增韧PP的作用。在OREC添加2phr时，POE／OREC／PP复合材料的强度大于相同用量的POE／PP二元体系的强度。在三元体系中，当POE用量15phr时，复合材料的冲击强度比纯PP提高204％，比POE／PP提高15．6％，拉伸强度比纯PP下降15．6％，比POE／PP提高22．6％。扫描电子显微镜分析(SEM)表明，三元体系呈现多相分散，在研究范围内，分散相尺寸越大，粒径分布越宽，复合材料的韧性越高。     

四氢呋喃聚醚型聚氨酯预聚体增韧双酚A型氰酸酯树脂

以本体树脂双酚A型氰酸酯树脂(BCE)为扩链剂,改性四氢呋喃聚醚型聚氨酯预聚体(A)得到改性预聚体BA,用BA与BCE共聚共混以改善BCE树脂的韧性。确定了BCE/BA的固化工艺,考察了共聚共混体系静态力学性能、动态力学性能及热性能。结果表明,用BA与BCE树脂共聚共混,可有效提高氰酸酯树脂基体的韧性和强度。当BA用量为10份时,BCE/BA体系的冲击韧性比纯树脂提高了64%;当BA用量为20份时,增强增韧效果最佳,BCE/BA体系的冲击韧性可达14.5 kJ.m-2,比纯树脂提高了142%;弯曲强度为128 MPa,比纯树脂提高了23%。     

Influence of Matrixes on Microstructure and Properties of CTBN Toughened Epoxy Resins

The influence of the type of epoxy resins (E-51, F-51) on the mechanical properties and mi-crostructure of carboxyl-terminated butadiene nitrile rubber ( CTBN) toughened epoxy resins was investigated by determination of adhesive strength and toughness as well as observation of scanning electron microstructure (SEM). The resuhs indicate that the adhesive strength of CTBN toughened E-51 system is superior to CTBN toughened F-51 system. However, CTBN toughened E-51 system is inferior to CTBN toughened F-51 system in the toughness . This difference is related to the microstructure of two toughened systems . For CTBN toughened F-51, larger cavities and rubber particles are found in the system.. The larger cavities easily cause stress concentration and result in decrease of the adhesive strength. While the larger rubber particles may better terminate the development of crazing and shear banding and result in increase of the toughness .     

液体端羧基丁腈橡胶改性氰酸酯树脂的结构与性能

采用液体端羧基丁腈橡胶(CTBN)对氰酸酯树脂(CE)进行共混改性。利用红外光谱、扫描电子显微镜等手段表征共混物的结构,测定其力学性能、耐热性等。实验结果表明,液体端羧基丁腈橡胶改性氰酸酯树脂可形成典型的海岛状共混结构;当面均粒径为2～3μm时,增韧效果最佳;当CTBN加入10份时,冲击强度提高150%,最大失重率所对应的温度只下降3.5℃。     

Isocyanate-terminated Polyethers Toughened Epoxy Resin:Chemical Modification,Thermal Properties,and Mechanical Strength

The toughening of the diglycidyl ether of bisphenol A epoxy resin with isocyanate-terminated polyethers(ITPE)was investigated.The progress of the reaction and the structural changes during modification process were studied using FTIR spectroscopy.The studies support the proposition that TDI(tolylene diisocyanate)acts as a coupling agent between the epoxy and polyethers,forming a urethane linkage with the former and the latter,respectively.Me THPA-cured ER/ITPs blends were characterized using dynamic mechanical analysis(DMA)and thermogravimetric analysis(TGA).It is indicated the glass transition temperature(T g )of systems was lower than the T g of pure epoxy resin and overfull ITPE separated from the modified epoxy resin and formed another phase at an ITPE-content of more than 10wt%.The thermal stability was decreased by the introduction of ITPE.The impact strength and the flexural strength of the cured modified-epoxy increased with increasing the ITPE content and a maximum plateau value of about 24.03 kJ/m2 and 130.56 MPa was measured in 10wt%ITPE.From scanning electron microscopy(SEM)studies of the fractrue surfaces of ER/ITPE systems,the nature of the micromechanisms responsible for the increases in toughness of the systems was identified.     

玄武岩短纤维增强环氧树脂复合材料的研究

以环氧树脂为基体、玄武岩短纤维为增强材料,制备了玄武岩短纤维/环氧树脂复合材料.研究了不同玄武岩短纤维含量对复合材料拉伸强度和耐磨性能的影响,采用扫描电子显微镜（SEM）观察了复合材料的断面形貌和磨损表面形貌,分析了磨损机制.结果表明,玄武岩短纤维/环氧树脂复合材料的抗拉强度和耐磨性能与纯环氧树脂相比均有不同程度的改善和提高,当玄武岩短纤维的含量为8%时,复合材料的拉伸强度最大;当玄武岩短纤维的含量为6%时,磨损率最低.随着玄武岩短纤维含量的增加,复合材料的磨损机制由黏着磨损向磨粒磨损转化.     

碳纤维上电聚合噻吩对复合材料性能的影响

为了改善碳纤维与树脂基体之间的界面性能,以噻吩为单体,采用循环伏安法对碳纤维进行电化学聚合改性.利用扫描电子显微镜研究了电化学聚合改性前后碳纤维的表面结构变化,采用电脑伺服控制材料试验机测试了碳纤维增强环氧树脂复合材料的力学性能.结果表明,当噻吩浓度为0.4 mol/L时,峰值电流增加幅度最大,电聚合效果最佳.当循环次数达到60次时,碳纤维表面电化学聚合反应完全,碳纤维/环氧树脂复合材料的层间剪切强度可由13.46 MPa增加到23.79 MPa,提高约76.75%.电化学聚合后大量片层状聚噻吩聚合物在碳纤维表面聚集,碳纤维与环氧树脂基体紧密结合,界面性能明显提高.     

Isocyanate-terminatcd Polyethers Toughened Epoxy Resin： Chemical Modification, Thermal Properties, and Mechanical Strength

The toughening of the diglycidyl ether of bisphenol A epoxy resin with isocyanateterminated polyethers （ITPE） was investigated. The progress of the reaction and the structural changes during modification process were studied using FTIR spectroscopy. The studies support the proposition that TDI （tolylene diisocyanate） acts as a coupling agent between the epoxy and polyethers, forming a urethane linkage with the former and the latter, respectively. Me THPA-cured ER/ITPs blends were characterized using dynamic mechanical analysis （DMA） and thermogravimetric analysis （TGA）. It is indicated the glass transition temperature （T） of systems was lower than the T of pure epoxy resin and overfull ITPE separated from the modified epoxy resin and formed another phase at an ITPE-content of more than 10wt%. The thermal stability was decreased by the introduction of ITPE. The impact strength and the flexural strength of the cured modifiedepoxy increased with increasing the ITPE content and a maximum plateau value of about 24.03 kJ/m^2 and 130.56 MPa was measured in 10wt% ITPE. From scanning electron microscopy （SEM） studies of the fractrue surfaces of ER/ITPE systems, the nature of the micromechanisms responsible for the increases in toughness of the systems was identified.     

Synthesis and properties of perfluorinated alkyl silicone oil modified epoxy resin

Perfluorinated alkyl silicone oil （PFASO） was successfully synthesized from N-ethyl-N- hydroxylethyl perfluorinated octane sulfonamide, succinie anhydride and amino silicone oil by esterification and amide reaction at moderate temperature in the presence of different catalysts. The chemical structure of the synthesized samples was characterized by Fourier transform infrared spectroscopy （FT-IR）, the relative molecular mass（MM） and molecular mass distribution（MMD） of PFASO were tested by gel filtration chromatography（GFC）. A commercial epoxy resin （DGEBA） was modified with PFASO, with the content of PFASO 1-5 phr. Thermo-gravimetric analysis （TGA）, impact tests, scanning electron microscope （SEM） and water contact angle test were applied to provide accurate results on the thermal stability, toughness and hydrophobicity of PFASO/epoxy complex. The experimental results reveal that epoxy resins can be successfully modified by adding a small amount of as-synthesized modifiers via simple direct mixing, and verify that the as-synthesized modifier can improve the toughness and hydrophobicity of epoxy resin without sacrificing its thermal properties.     

Synthesis and Properties of Novel Epoxidized Soybean Oil-modified Phenolic Resin/Montmorillonite Nanoeomposites

The novel epoxidized soybean oil-modified-phenolic resin/clay nanocomposites(ESO-M-PR/CN)was prepared.The coupling agent-benzyldimethylphenylammonium chloride [C6H5CH2N+(CH3)2C6H5Cl-,B2MP]was adopted to modify the interface between the organic and inorganic phases.The effect of the nanocomposite structure on its physical and chemical properties was discussed.During the synthesizing process of ESO-M-PR/CN,the phenol hydroxyl was etherified by ESO or ESO epoxy resin prepolymer to provide long ESO epoxy segments.Long ESO epoxy resin chain segments enhanced the crosslink density of ESO-M-PR/CN.The thermal and mechanical properties exhibit a significant improvement.The temperature at which a weight loss of 5%Occurs increases from 287.1℃to 402.3℃.The flexural strength increases by 25%,while the flexural modulus increases by 39%.Moreover,the properties of resin were enhanced by the effect of the inorganic nanoparticles,while the size of the nanomontmorillonites in the phenolic resin was characterized with a scanning electron microscope.The particle size of inorganic montmorillonites in the modified system is less than 100 nm.     

水镁石/硼酸锌复合阻燃环氧树脂的制备与性能

针对环氧树脂在添加普通水镁石阻燃剂后力学性能恶化的问题,通过对水镁石的改性和复配制备了一种新型阻燃剂.通过SEM观察水镁石粉体及阻燃环氧树脂断面的表面形貌,利用弯曲强度测试考察阻燃环氧树脂的力学性能,测定氧指数考察其阻燃性能.结果表明,水镁石用量为30%时阻燃EP性能最好.用硅烷偶联剂Ⅰ和Z6173改性,阻燃EP的弯曲强度和氧指数分别为5.21 M Pa、28.9%和4.82 M Pa、29.1%.用6份的硼酸锌与硅烷偶联剂Ⅰ改性的水镁石复配制得的复合阻燃剂,其制备成的阻燃EP的弯曲强度和氧指数最高达到4.85 MPa和29.3%.     

硬质低发泡PVC流变性能分析

用RM-200转矩流变仪对不同配方的硬质低发泡聚氯乙烯(PVC)的流变性能进行了分析.结果表明:PVC(S-700)比PVC(S-800)树脂的粘度小,流动性能好,容易塑化,热稳定性能好;随AC复合发泡剂用量增加,物料粘度下降,流动性提高,用量超过0.8份时,物料的粘度会提高;小份量的加工助剂ACR-201使PVC物料的塑化时间明显缩短,3份以上时,对塑化时间影响不明显;发泡调节剂ZB-530能够促进PVC塑化,提高熔体的强度;成核剂CaCO3小于5份时,能降低熔体粘度改善塑化行为,超过5份时,熔体粘度随份量增加而增大,塑化时间增长,不利于塑化.     

端活性聚丙二醇对环氧树脂的增韧改性

以端羟基聚丙二醇为基础合成了端羧基和端环氧基聚丙二醇,对不同端基聚丙二醇改性环氧树脂体系进行了DSC、DMA、冲击性能和冲断面SEM研究。随聚丙二醇端活性基与环氧树脂反应性的增强,固化体系更倾向于形成均相结构,环氧树脂固化物玻璃化温度降低更多。端羟基和端环氧聚丙二醇都能明显提高环氧树脂的冲击强度。综合分析测试结果表明聚丙二醇是通过增塑方式对环氧树脂进行增韧,而端环氧基聚丙二醇是通过提高交联网络柔性的方式对环氧树脂进行增韧。     

电工环氧树脂固化工艺研究

电工环氧树脂的固化剂选用甲基六氢苯酐（MHHPA）酸酐体系,并对固化浇注工艺及填料改性处理固化体系进行研究.固化剂、填料等改性剂的用量,固化体系的配方配比、工艺特性等方面对固化产物电学性能、机械性能都产生一定的影响.固化体系采用环氧树脂100份,甲基六氢苯酐86份,咪唑0.8份,二氧化钛3份,偶联剂KH5501份时,固化产物抗拉强度61.972 MPa,冲击强度6.172 kJ/m^2,介电常数2.268,介电损耗角正切0.001 9,体积电阻率3.076×1015.此种环氧树脂材料可适用于高压大电流开关、高压变压器绝缘子及高压组合电器等高科技领域,满足其在电工工业领域的应用要求.     

树脂增强选择性激光烧结多孔金属件的研究

针对选择性激光烧结(SLS)间接方法成型的金属零件形坯,经脱脂和高温烧结后形成的零件存在大量孔隙和空洞,其致密度和强度都较低,不能满足实际应用要求的问题,采用改性耐高温环氧树脂浸渗零件烧结坯的方法,使多孔金属件致密化,并粘结内部金属网架,提高零件的机械性能.对浸渗烧结坯的拉伸强度的测试和扫描电镜(SEM)以及热失重(TGA)的分析结果表明,浸渗树脂后的烧结坯拉伸强度提高了约4倍;改性环氧树脂和金属网架粘结在一起,形成一个密实的网络结构,致密度大幅提高;零件可在200℃的温度下使用.该方法可以制造注塑模具和功能零件.     

Strength of copolymer grouting material based on orthogonal experiment

Using the orthogonal experimental design method involving three factors and three levels, the flexural strength and the compressive strength of copolymer grouting material were studied with different compositions of water-cement ratio (mass fraction of water to cement), epoxy resin content, and waterborne epoxy curing agent content. By orthogonal range and variance analysis, the orders of three factors to influence the strength, the significance levels of different factors, and the optimized compound ratio scheme of copolymer grouting material mixture at different curing ages were determined. An empirical relationship among the strength of copolymer grouting material, the water-cement ratio, the epoxy resin content, and the waterborne epoxy curing agent content was established by multivariate regression analysis. The results indicate that water-cement ratio is the most principal and significant influencing factor on the strength. Epoxy resin content and waterborne epoxy curing agent content also have a significant influence on the strength. But epoxy resin content has a greater influence on the 7-day and 28-day flexural strength, and waterborne epoxy curing agent content has a greater influence on the 3-day flexural strength and the compressive strength. The copolymer grouting material with water-cement ratio of 0.4, epoxy resin content of 8% (mass fraction) and waterborne epoxy curing agent content of 2% (mass fraction) is the best one for repairing of cement concrete pavement. The flexural strength and the compressive strength have good correlation, and the ratio of compressive strength to flexural strength is between 1.0 and 3.3. Foundation item: Projects(40728003, 40772180, 40802064) supported by the National Natural Science Foundation of China; Project (07JJ4012) supported by the Hunan Provincial Natural Science Foundation of China; Project(20080430680) supported by China Postdoctoral Science Foundation; Project(B308) supported by Shanghai Leading Academic Discipline Project     

端异氰酸酯基聚醚接枝环氧树脂的性能研究

合成了端异氰酸酯基聚醚（ITPs）改性双酚A型环氧树脂，通过红外光谱（IR）、动态热机械分析（DMA）研究了ITPs和EP之间的化学反应及改性环氧树脂酸酐固化体系的热性能，并测试了固化体系的力学性能。结果表明：ITPs作为枝链接枝到环氧树脂上：随着加入ITPs质量分率增加，其固化体系的冲击强度和弯曲强度上升，当ITPs含量为10％时，两者达到最大值：动态热机械分析（DMA）结果表明改性环氧树脂固化体系的玻璃化转变温度（Tg）随ITPs的含量增大而降低：当ITPs质量分率大于15%时，过量的ITPs与改性环氧树脂会形成相分离。     

环氧树脂/蒙脱土纳米复合材料的制备及性能研究

采用双子季铵盐对蒙脱土进行有机化处理，再与环氧树脂进行插层复合制备了环氧树脂／蒙脱土复合材料、借助XRD和FTIR等手段对改性蒙脱土进行了表征，对复合材料的力学性能进行测试。结果表明，改性使蒙脱土层间距增大，有机蒙脱土的加入改善了环氧树脂基体的力学性能，当有机蒙脱土质量含量为1％时，其弯曲强度、冲击强度等力学性能得到了最大的提高。